Method for producing epoxyalkane, and solid oxidation catalyst

ABSTRACT

The present invention provides: a method for producing an epoxyalkane capable of obtaining an epoxide in a high yield while attaining a high olefin conversion rate and a high selectivity for epoxides even when an olefin includes a long carbon chain, and a solid oxidation catalyst used in the method. The method for producing an epoxyalkane of the present invention comprises reacting an olefin with an oxidant in the presence of a solid oxidation catalyst, wherein the solid oxidation catalyst comprises a transition metal and a carrier that supports the transition metal, and the carrier is a metal oxide having a silyl group represented by the following general formula (1):R1R2R3Si—  (1)wherein R1, R2, and R3 are each independently a single bond, a hydrocarbon group, a halogenated hydrocarbon group, an alkoxy group, or a halogen, and at least one of R1, R2, and R3 is a hydrocarbon group having 3 or more carbon atoms or a halogenated hydrocarbon group having 3 or more carbon atoms.

TECHNICAL FIELD

The present invention relates to a method for producing an epoxyalkaneby reacting an olefin with hydrogen peroxide in the presence of a solidoxidation catalyst, and to the solid oxidation catalyst used in themethod.

BACKGROUND ART

A method of epoxidizing an olefin using hydrogen peroxide is known. Thismethod generally has problems that both the olefin conversion rate andthe selectivity for epoxides are low.

For aiming at selectively producing only epoxides, JP-A-2001-17864discloses a method for producing an epoxidized product using anepoxidation catalyst that is a salt obtained by the reaction between:(1) a surface-treated carrier obtained by reacting (a) an activatedcarbon or an inorganic solid having a functional group capable of beingreacted with a silane coupling agent, with (b) a silane coupling agenthaving an alkyl group substituted with a functional group capable ofbeing reacted with a tertiary amine to form a quaternary ammonium salt,and reacting the reaction product with a tertiary amine or a cyclicamine; and (2) a heteropolyacid having a group V atom in the periodictable and a tungsten atom in its molecule.

SUMMARY OF THE INVENTION

However, in the method for producing an epoxidized product ofJP-A-2001-17864, it is found that when an olefin includes a short carbonchain, the olefin had a high conversion rate and a high selectivity forepoxides, but when the olefin includes a long carbon chain, thecatalytic activity of the epoxidation catalyst was greatly reduced andthe epoxidation reaction hardly proceeded or the olefin conversion ratewas greatly reduced.

The present invention has been made in view of the above circumstances,and provides a method for producing an epoxyalkane capable of obtainingan epoxide in a high yield while attaining a high olefin conversion rateand a high selectivity for epoxides even when an olefin includes a longcarbon chain, and a solid oxidation catalyst used in the method.

As a result of intensive studies, the present inventor has found thatthe above problems can be solved by the following method for producingan epoxyalkane, and the following solid oxidation catalyst.

That is, the present invention is related to a method for producing anepoxyalkane, which method comprises reacting an olefin with an oxidantin the presence of a solid oxidation catalyst, wherein

the solid oxidation catalyst comprises a transition metal and a carrierthat supports the transition metal, and

the carrier is a metal oxide having a silyl group represented by thefollowing general formula (1):

R¹R²R³Si—  (1)

wherein R¹, R², and R³ are each independently a single bond, ahydrocarbon group, a halogenated hydrocarbon group, an alkoxy group, ora halogen, and at least one of R¹, R², and R³ is a hydrocarbon grouphaving 3 or more carbon atoms or a halogenated hydrocarbon group having3 or more carbon atoms.

Also, the present invention is related to a solid oxidation catalystthat is used in a method for producing an epoxyalkane by reacting anolefin with an oxidant, wherein

the solid oxidation catalyst comprises a transition metal and a carrierthat supports the transition metal, and

the carrier is a metal oxide having a silyl group represented by thefollowing general formula (1):

R¹R²R³Si—  (1)

wherein R¹, R², and R³ are each independently a single bond, ahydrocarbon group, a halogenated hydrocarbon group, an alkoxy group, ora halogen, and at least one of R¹, R², and R³ is a hydrocarbon grouphaving 3 or more carbon atoms or a halogenated hydrocarbon group having3 or more carbon atoms.

According to the method for producing an epoxyalkane of the presentinvention, a desired epoxide can be obtained in a high yield whileattaining a high olefin conversion rate and a high selectivity forepoxides even when a raw material olefin has a long carbon chain.

MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

Solid Oxidation Catalyst

The solid oxidation catalyst of the present invention comprises atransition metal and a carrier that supports the transition metal, and

the carrier is a metal oxide having a silyl group represented by thefollowing general formula (1):

R¹R²R³Si—  (1)

wherein R¹, R², and R³ are each independently a single bond, ahydrocarbon group, a halogenated hydrocarbon group, an alkoxy group, ora halogen, and at least one of R¹, R², and R³ is a hydrocarbon grouphaving 3 or more carbon atoms or a halogenated hydrocarbon group having3 or more carbon atoms.

The transition metal is supported on the carrier in the form of a simplesubstance, a compound, or an ion.

The transition metal is a metal element of groups 3 to 12 of theperiodic table, and specific examples of the transition metal include agroup 3 element (Sc, Y, etc.), a group 4 element (Ti, Zr, Hf), a group 5element (V, Nb, Ta), a group 6 element (Cr, Mo, W), a group 7 element(Mn, Tc, Re), a group 8 element (Fe, Ru, Os), a group 9 element (Co, Rh,Ir), a group 10 element (Ni, Pd, Pt), a group 11 element (Cu, Ag, Au),and a group 12 element (Zn, Cd, Hg). These metals may be used alone orin combination of two or more thereof. Of these, a metal element ofgroups 4 to 8 is preferred, a group 6 metal element is more preferred,and W is still more preferred.

The compound of the transition metal is not particularly limited, andexamples thereof include hydroxides, oxides, halides (e.g., fluorides,chlorides, bromides, iodides, etc.), oxo acid salts (e.g., nitrates,sulfates, phosphates, borates, carbonates, etc.), isopoly acid salts,heteropoly acid salts, and organic acid salts (e.g., acetates,propionates, cyanides, naphthenates, stearates, alkylsulfonates,arylsulfonates, etc.) of the transition metals.

The transition metal compound is preferably a tungsten compound from theviewpoint of catalytic activity. Examples of the tungsten compoundinclude tungstic acids or salts thereof (e.g. tungstic acid, sodiumtungstate, potassium tungstate, lithium tungstate, ammonium tungstate,etc.); dodecatungstates (e.g. sodium dodecatungstate, potassiumdodecatungstate, ammonium dodecatungstate, etc.); and heteropolyacids orsalts thereof containing tungsten atoms (e.g. phosphotungstic acid,sodium phosphotungstate, silicotungstic acid, sodium silicotungstate,phosphovanadotungstate, phosphomolybdotungstate, etc.). These may beused alone or in combination of two or more thereof. Of these, tungsticacid or a salt thereof is preferable.

The carrier is a metal oxide having a silyl group represented by thefollowing general formula (1):

R¹R²R³Si—  (1)

wherein R¹, R², and R³ are each independently a single bond, ahydrocarbon group, a halogenated hydrocarbon group, an alkoxy group, ora halogen, and at least one of R¹, R², and R³ is a hydrocarbon grouphaving 3 or more carbon atoms or a halogenated hydrocarbon group having3 or more carbon atoms. The hydrophobicity of the carrier can beadjusted by the type of organic groups (for example, hydrocarbon group,halogenated hydrocarbon group, and alkoxy group) contained in the silylgroup. As a result, the olefin conversion rate can be increased evenwhen the olefin has a long carbon chain.

The metal oxide is not particularly limited, but from the viewpoint ofcatalytic activity, an oxide containing a metal element having a periodof 3 to 5 cycles in the periodic table is preferable, an oxidecontaining one or more metal elements selected from Mg, Al, Si, Ti, Fe,Zn, Ga, Y, Zr, and Sn is more preferable, and an oxide containing Al isstill more preferable. These may be used alone or in combination of twoor more thereof.

Specific examples of the metal oxide include silica, alumina, titania,magnesia, zirconia, aluminum phosphate, silicoaluminophosphate, andmetallic aluminum phosphate (the metals include, for example, titanium,iron, magnesium, zinc, manganese, cobalt, etc.). These metal oxides maybe used alone or in combination of two or more thereof.

Examples of the silica include glassy silica, quartz, diatomaceousearth, amorphous silica, silica gel, silica powder, silica sol, variouscoated silica fine particles (zeolite, etc.) whose silica surface iscoated with aluminum or the like, silica-coated fine particles in whichthe surface of resin particles or metal oxide sol is coated with silica,spherical silica fine particles, rod-shaped silica fine particles, andnecklace-shaped silica fine particles in which spherical silica isconnected.

Examples of the alumina include α-alumina, gibbsite, bayerite, boehmite,β-alumina, γ-alumina, and amorphous alumina.

Examples of the titania include rutile-type titania and anatase-typetitania.

Examples of the magnesia include magnesium carbonate (magnesite), moltenmagnesia obtained by melting or calcining magnesium carbonate extractedfrom seawater, sintered magnesia, light-baked magnesia, and calcinedmagnesia.

Examples of the zirconia include partially stabilized zirconiacontaining ZrO₂ as a main component and one or more stabilizers such asCaO, MgO, or Y₂O₃.

The metal oxide may be a composite with phosphonic acid. Here, thecomposite means a metal oxide in which a part of the skeletal structureis replaced with phosphonic acid.

The metal oxide preferably contains phosphoric acid from the viewpointof forming a composite with phosphonic acid, and more preferablycontains Al and/or phosphoric acid from the viewpoint of catalyticactivity and of forming a composite with phosphonic acid, and is stillmore preferably aluminum phosphate from the viewpoint of catalyticactivity and of forming a composite with a phosphonic acid.

The phosphonic acid used is not particularly limited, but is preferablyan organic phosphonic acid having a saturated or unsaturated hydrocarbongroup having 1 or more and 18 or less carbon atoms, more preferably oneor more selected from an alkylphosphonic acid having an alkyl group of 2to 18 carbon atoms and an aryl phosphonic acid, and still morepreferably an alkylphosphonic acid having an alkyl group of 2 to 18carbon atoms, from the viewpoint of catalytic activity. The alkyl grouphaving 1 or more and 18 or less carbon atoms is not particularlylimited, and examples thereof include a methyl group, an ethyl group, apropyl group, a butyl group, a pentyl group, a hexyl group, a heptylgroup, a 2-ethylhexyl group, an octyl group, a nonyl group, a decylgroup, an undecyl group, a dodecyl group, a tridecyl group, a tetradecylgroup, a pentadecyl group, a hexadecyl group, a heptadecyl group, and anoctadecyl group. Examples of the aryl group include a phenyl group, abenzyl group, a tolyl group, a xylyl group, a naphthyl group, and abiphenyl group. When the phosphonic acid is an organic phosphonic acid,the hydrophobicity of the carrier can be adjusted by the type of theorganic group (for example, hydrocarbon group, halogenated hydrocarbongroup, and alkoxy group) of the organic phosphonic acid. As a result,the olefin conversion rate can be increased even when the carbon chainof the olefin is long.

Examples of the method for preparing the composite of the metal oxideand the phosphonic acid include a precipitation method and a method ofimpregnating a metal oxide with phosphonic acid, and the precipitationmethod is preferred.

Hereinafter, as a specific example of the method for preparing thecomposite, a method for preparing a composite of aluminum phosphate andan organic phosphonic acid (RPOO₂AlPO₄) by a precipitation method willbe described.

In the precipitation method, first, an aqueous solution (S) containing awater-soluble aluminum salt (for example, Al(NO₃)₃.9H₂O, etc.),phosphoric acid, and an organic phosphonic acid is mixed with an alkali(T). When the solubility of the organic phosphonic acid is poor, theaqueous solution (S) may be prepared by appropriately adding a solventsuch as alcohol or acetone.

The molar ratio (Al/P) of Al in the water-soluble aluminum salt to P inthe phosphoric acid and organic phosphonic acid is preferably 0.6 ormore, more preferably 0.7 or more, still more preferably 0.8 or more,even still more preferably 0.9 or more, and is preferably 10 or less,more preferably 5 or less, still more preferably 2 or less, even stillmore preferably less than 1, from the viewpoint of reactivity.

From the viewpoint of reactivity, the molar ratio of the organicphosphonic acid to the phosphoric acid (organic phosphonicacid/phosphoric acid) is preferably 0.05 or more, more preferably 0.1 ormore, still more preferably 0.2 or more, even still more preferably 0.3or more, and is preferably 5 or less, more preferably 3 or less, stillmore preferably 1 or less, even still more preferably 0.5 or less.

The alkali (T) is not particularly limited, and examples thereof includeinorganic bases such as sodium hydroxide, potassium hydroxide, sodiumcarbonate, potassium carbonate, sodium hydrogen carbonate, and potassiumhydrogen carbonate, ammonia, and urea. From the viewpoint of reactivity,ammonia is preferable. These alkalis (T) are usually used as an aqueoussolution.

The method of mixing the aqueous solution (S) and the alkali (T) is notparticularly limited, but from the viewpoint of reactivity, a method ofdropping the alkali (T) into the aqueous solution (S) is preferable.From the viewpoint of reactivity and productivity, the dropping time ispreferably 0.5 hours or more, more preferably 1 hour or more, still morepreferably 2 hours or more, even still more preferably 3 hours or more,and is preferably 15 hours or less, more preferably 10 hours or less,still more preferably 5 hours or less. The reaction temperature ispreferably 20° C. or higher, more preferably 25° C. or higher, and ispreferably 80° C. or lower, more preferably 60° C. or lower, still morepreferably 40° C. or lower, from the viewpoint of reactivity andproductivity.

By mixing the aqueous solution (S) and the alkali (T) and adjusting thepH, a precipitate of a composite (RPOO₂AlPO₄) of aluminum phosphate withan organic phosphonic acid can be obtained. From the viewpoint ofreactivity, the pH in the pH adjustment is preferably 4.0 or more, morepreferably 4.5 or more, still more preferably 5.0 or more, and ispreferably 10.0 or less, more preferably 8.0 or less, still morepreferably 6.0 or less.

The precipitate is preferably aged in the reaction solution. The agingtime is preferably 0.5 hours or more, more preferably 1 hour or more,and is preferably 10 hours or less, more preferably 5 hours or less,still more preferably 3 hours or less, from the viewpoint of reactivityand productivity.

After that, the precipitate is filtered, washed with water as needed,and dried.

The dried precipitate may be calcined. From the viewpoint of reactivity,the calcination temperature is preferably 250° C. or higher, morepreferably 300° C. or higher, still more preferably 350° C. or higher,and is preferably 500° C. or lower, more preferably 450° C. or lower,still more preferably 400° C. or lower. From the viewpoint of reactivityand productivity, the calcination time is preferably 1 hour or more,more preferably 2 hours or more, still more preferably 3 hours or more,and is preferably 10 hours or less, more preferably 7 hours or less,still more preferably 5 hours or less. The atmosphere at the time ofcalcination is not particularly limited, but from the viewpoint ofreactivity, the calcination is preferably carried out in the presence ofair or oxygen.

The shape of the carrier is not particularly limited, and examplesthereof include powders, granules, noodles, and pellets.

When the carrier is in the form of a powder, the average particle sizeis preferably 1 μm or more, more preferably 3 μm or more, still morepreferably 5 μm or more, even still more preferably 7 μm or more, and ispreferably 300 μm or less, more preferably 200 μm or less, still morepreferably 100 μm or less, even still more preferably 30 μm or less,from the viewpoint of catalytic activity.

When the carrier is in the form of granules, the average particle sizeis preferably 0.2 mm or more, more preferably 0.4 mm or more, still morepreferably 0.6 mm or more, and is preferably 2.0 mm or less, morepreferably 1.3 mm or less, still more preferably 0.8 mm or less, fromthe viewpoint of catalytic activity and ease of recovery.

When the carrier is in the form of a noodle, the diameter is preferably1.0 mm or more, more preferably 1.2 mm or more, still more preferably1.4 mm or more, and is preferably 2.5 mm or less, more preferably 2.0 mmor less, still more preferably 1.5 mm or less, from the viewpoint ofcatalyst strength and catalytic activity.

When the carrier is in the form of a noodle, the length is preferably 2mm or more, more preferably 3 mm or more, and is preferably 8 mm orless, more preferably 6 mm or less, still more preferably 4 mm or less,from the viewpoint of uniformity at the time of filling and catalyststrength.

When the carrier is in the form of a pellet, the length is preferably1.5 mm or more, more preferably 2.0 mm or more, still more preferably2.5 mm or more, and is preferably 5.0 mm or less, more preferably 4.0 mmor less, still more preferably 3.0 mm or less, from the viewpoint ofcatalyst strength and catalytic activity.

The specific surface area of the carrier is preferably 30 m²/g or more,more preferably 50 m²/g or more, still more preferably 80 m²/g or more,and is preferably 250 m²/g or less, more preferably 190 m²/g or less,still more preferably 140 m²/g or less, from the viewpoint of catalyticactivity and selectively obtaining epoxides.

The average pore diameter of the carrier is preferably 2 nm or more,more preferably 3 nm or more, still more preferably 4 nm or more, and ispreferably 15 nm or less, more preferably 10 nm or less, still morepreferably 7 nm or less, from the viewpoint of catalytic activity andselectively obtaining epoxides.

The solid oxidation catalyst of the present invention can be prepared,for example, by supporting the transition metal on the metal oxide andthen silylating the metal oxide with a silylating agent.

The method for supporting the transition metal on the metal oxide is notparticularly limited, and known methods can be adopted and examplesthereof include a precipitation method, an impregnation method, aspraying method, an adsorption method, and a pore filling method, amongwhich an impregnation method is preferred.

Hereinafter, as a specific example, a method for supporting tungsticacid on the metal oxide by an impregnation method will be described.

In the impregnation method, first, tungstic acid and an alkali are mixedto prepare an aqueous tungstic acid solution. The alkali is notparticularly limited, and examples thereof include inorganic bases (e.g.sodium hydroxide, potassium hydroxide, sodium carbonate, potassiumcarbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate),ammonia, and urea. From the viewpoint of reactivity, ammonia ispreferred. These alkalis are usually used as an aqueous solution. Then,the prepared aqueous tungstate solution and the metal oxide are mixed tosupport the tungstic acid on the metal oxide. If the metal oxide isdifficult to disperse in the aqueous tungstate solution, a solvent suchas alcohol or acetone may be added as appropriate.

After that, water and solvent in the aqueous solution are distilled off.The metal oxide supporting tungstic acid (hereinafter, referred to asW-supported metal oxide) is washed with water if necessary and dried.The W-supported metal oxide after drying may be pulverized.

Alternatively, the W-supported metal oxide after drying may be calcined.The calcination temperature is preferably 150° C. or higher, morepreferably 200° C. or higher, still more preferably 300° C. or higher,and is preferably 500° C. or lower, more preferably 450° C. or lower,still more preferably 400° C. or lower, from the viewpoint of catalyticactivity and selectively obtaining epoxides. The calcination time ispreferably 1 hour or more, more preferably 2 hours or more, still morepreferably 3 hours or more, and is preferably 10 hours or less, morepreferably 7 hours or less, still more preferably 5 hours or less, fromthe viewpoint of catalytic activity and selectively obtaining epoxides.The atmosphere at the time of calcination is not particularly limited,but the calcination is preferably carried out in the presence of air oroxygen from the viewpoint of catalytic activity and selectivelyobtaining epoxides.

Examples of the silylating agent include a silylating agent representedby the following general formula (2):

R¹R²R³SiX   (2)

wherein R¹, R², and R³ are each independently a hydrocarbon group, ahalogenated hydrocarbon group, an alkoxy group, or a halogen; at leastone of R¹, R², and R³ is a hydrocarbon group having 3 or more carbonatoms or a halogenated hydrocarbon group having 3 or more carbon atoms;and X is an alkoxy group or a halogen.

The hydrocarbon group is not particularly limited, and examples thereofinclude a saturated or unsaturated aliphatic hydrocarbon group, asaturated or unsaturated alicyclic hydrocarbon group, and an aromatichydrocarbon group. The number of carbon atoms of each of the aliphatichydrocarbon group and the alicyclic hydrocarbon group is notparticularly limited, but from the viewpoint of catalytic activity andselectively obtaining an epoxide, the number of carbon atoms of saidgroups is preferably 3 or more, more preferably 6 or more, still morepreferably 8 or more, and is preferably 22 or less, more preferably 18or less, still more preferably 12 or less. Examples of the aromatichydrocarbon group include a phenyl group, a benzyl group, a tolyl group,a xylyl group, a naphthyl group, and a biphenyl group.

The halogenated hydrocarbon group is not particularly limited, andexamples thereof include those in which one or more hydrogens of thehydrocarbon group are substituted with halogen{s} such as fluorine,chlorine, bromine, and iodine.

The alkoxy group is not particularly limited, and examples thereofinclude an alkoxy group having 1 to 6 carbon atoms. From the viewpointof reactivity with the metal oxide, the alkoxy group has preferably 4 orless carbon atoms, more preferably 2 or less carbon atoms, still morepreferably 1 carbon atom.

The halogen is not particularly limited, and examples thereof includefluorine, chlorine, bromine, and iodine, and chlorine is preferable fromthe viewpoint of reactivity with the metal oxide.

At least one of R¹, R², and R³ is a hydrocarbon group having 3 or morecarbon atoms or a halogenated hydrocarbon group having 3 or more carbonatoms, and from the viewpoint of catalytic activity and selectivelyobtaining an epoxide, the number of carbon atoms is preferably 6 ormore, more preferably 8 or more, and is preferably 22 or less, morepreferably 18 or less, still more preferably 12 or less.

Examples of the silylating agent include (CH₃O)₃SiC₃H₇, (CH₃O)₃SiC₄H₉,(CH₃O)₃SiC₅H₁₁ (CH₃O)₃SiC₆H₁₃, (CH₃O)₃SiC₇H₁₅, (CH₃O)₃SiC₈H₁₇,(CH₃O)₃SiC₉H₁₉, (CH₃O)₃SiC₁₀H₂₁, (CH₃O)₃SiC₁₁H₂₃, (CH₃O)₃SiC₁₂H₂₅,(CH₃O)₃SiC₁₃H₂₇, (CH₃O)₃SiC₁₄H₂₉, (CH₃O)₃SiC₁₅H₃₁, (CH₃O)₃SiC₁₆H₃₃,(CH₃O)₃SiC₁₇H₃₅, (CH₃O)₃SiC₁₈H₃₇, (CH₃O)₃Si(CH₂)₆CH═CH₂, and(CH₃O)₃SiCH₂CH₂(CF₂)₇CF₃.

The silylation treatment is not particularly limited and known methodscan be adopted. For example, a method of reacting a metal oxidesupporting a transition metal with the silylating agent in a solvent canbe mentioned. The solvent is not particularly limited, and examplesthereof include a non-polar organic solvent, preferably at least onenon-polar organic solvent selected from hexane, ether, benzene, andtoluene.

The blending amount of the silylating agent is preferably 0.05 parts bymass or more, more preferably 0.2 parts by mass or more, still morepreferably 0.4 parts by mass or more, even still more preferably 0.6parts by mass or more, and is preferably 40 parts by mass or less, morepreferably 30 parts by mass or less, still more preferably 20 parts bymass or less, even still more preferably 10 parts by mass or less,furthermore preferably 8 parts by mass or less, with respect to 100parts by mass of the metal oxide supporting the transition metal, fromthe viewpoint of reactivity with the metal oxide supporting thetransition metal.

The reaction temperature is not particularly limited, but is preferably70° C. or higher, more preferably 80° C. or higher, still morepreferably 90° C. or higher, and is preferably 120° C. or lower, morepreferably 110° C. or lower, from the viewpoint of reactivity.

The reaction time is not particularly limited, but is preferably 0.5hours or more, more preferably 1 hour or more, still more preferably 1.5hours or more, even still more preferably 2 hours or more, and ispreferably 30 hours or less, more preferably 20 hours or less, stillmore preferably 10 hours or less, even still more preferably 7 hours orless, from the viewpoint of reactivity.

After the reaction is completed, the produced solid oxidation catalystis filtered, washed with water if necessary, and dried. The solidoxidation catalyst after drying may be pulverized.

The amount of the transition metal (for example, W) supported in thesolid oxidation catalyst is preferably 0.5% by mass or more, morepreferably 1% by mass or more, still more preferably 3% by mass or more,even still more preferably 5% by mass or more, and is preferably 50% bymass or less, more preferably 25% by mass or less, still more preferably15% by mass or less, even still more preferably 10% by mass or less,from the viewpoint of catalytic activity and selectively obtainingepoxides.

The wetting tension of the solid oxidation catalyst is preferably 30mN/m or more, more preferably 40 mN/m or more, still more preferably 50mN/m or more, even still more preferably 55 mN/m or more, and ispreferably 73 mN/m or less, more preferably 70 mN/m or less, still morepreferably 65 mN/m or less, even still more preferably 60 mN/m or less,from the viewpoint of catalytic activity and selectively obtainingepoxides.

The catalytic specific surface area of the solid oxidation catalyst ispreferably 30 m²/g or more, more preferably 50 m²/g or more, still morepreferably 80 m²/g or more, and is preferably 250 m²/g or less, morepreferably 190 m²/g or less, still more preferably 140 m²/g or less,from the viewpoint of catalytic activity and selectively obtainingepoxides.

The average pore size of the solid oxidation catalyst is preferably 2 nmor more, more preferably 3 nm or more, still more preferably 4 nm ormore, and is preferably 15 nm or less, more preferably 10 nm or less,still more preferably 7 nm or less, from the viewpoint of catalyticactivity and selectively obtaining epoxides.

From the viewpoint of catalytic activity, the particle size of the solidoxidation catalyst is preferably 1 μm or more, more preferably 3 μm ormore, still more preferably 5 μm or more, even still more preferably 7μm or more, and is preferably 300 μm or less, more preferably 200 μm orless, still more preferably 100 μm or less, even still more preferably30 μm or less.

Production of Epoxyalkane

In the present invention, an epoxyalkane is produced by reacting anolefin with an oxidant in the presence of the solid oxidation catalyst.

The olefin is not particularly limited, and may be a linear, branched,monocyclic, bicyclic, or polycyclic unsaturated hydrocarbon, and may bea monoolefin, a diolefin, or a polyolefin. The olefin may have varioussubstituents containing halogen, oxygen, sulfur, or nitrogen atoms alongwith hydrogen and/or carbon atoms. The double bond may be at the end ofthe carbon chain or inside. If there are two or more double bonds, theymay be conjugated or non-conjugated. One type of olefin may be used, ortwo or more types of olefins may be used in combination.

The olefin is preferably a linear or branched unsaturated hydrocarbon.

The carbon number of the olefin (excluding the carbon number of thesubstituent) is not particularly limited, and is, for example, 2 or moreand 60 or less, preferably 8 or more, more preferably 12 or more, stillmore preferably 14 or more, even still more preferably 16 or more, andpreferably 22 or less, more preferably 20 or less, still more preferably18 or less. The method for producing an epoxyalkane of the presentinvention is suitable when the carbon number of the olefin is large.

Examples of the oxidant include a peroxide, a halogen acid or a saltthereof, a perhalogen acid or a salt thereof, and ozone. One type ofoxidant may be used, or a plurality of oxidants may be used incombination.

Examples of the peroxides include peracids or salts thereof, non-peracidtype organic peroxides, and non-peracid type inorganic peroxides.Examples of the peracid include percarboxylic acid, persulfuric acid,percarbonic acid, perphosphoric acid, and hypoperhalic acid. Examples ofthe percarboxylic acid include peracetic acid, perbenzoic acid, andmetachloroperbenzoic acid. Examples of the hypoperhalic acid includehypoperchloric acid, hypoperbromoic acid, and hypoperiodic acid.Examples of the non-peracid type organic peroxide include tert-butylhydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide,dimethyldioxirane, acetone peroxide, methyl ethyl ketone peroxide, andhexamethylene triperoxide diamine. Examples of the non-peracid typeinorganic peroxide include hydrogen peroxide, lithium peroxide, sodiumperoxide, potassium peroxide, and permanganate.

Examples of the halogen acid include chloric acid, bromic acid, andiodic acid. Examples of the perhalogen acid include perchloric acid,perbromic acid, and periodic acid.

Examples of the peracid salt, halogenic acid salt, perhalogen acid salt,and permanganic acid salt include salts of alkali metals such aslithium, sodium, and potassium, salts of alkaline earth metals such asmagnesium, calcium, and barium, other metal salts, and ammonium salts.

The oxidant is preferably a peroxide, more preferably hydrogen peroxide.

When the oxidant is hydrogen peroxide, its usage (solvents such aswater, ethanol, and ether and concentrations thereof) is notparticularly limited, and for example, an aqueous solution having ahydrogen peroxide concentration of 3 to 90% by mass is used. From theviewpoint of reactivity, the concentration of hydrogen peroxide ispreferably 10% by mass or more, more preferably 25% by mass or more,still more preferably 40% by mass or more, and is preferably 85% by massor less, more preferably 70% by mass or less, still more preferably 65%by mass or less.

The amount of the oxidant used is not particularly limited, but from theviewpoint of reactivity, the amount of the oxidant is preferably 0.2equivalents or more, more preferably 0.5 equivalents or more, still morepreferably 0.8 equivalents or more, even still more preferably 1.0equivalent or more, and is preferably 10 equivalents or less, morepreferably 5 equivalents or less, still more preferably 3 equivalents orless, even still more preferably 1.5 equivalents or less, with respectto 1 equivalent of the olefin.

The amount of the solid oxidation catalyst used is not particularlylimited, but is preferably 0.5 parts by mass or more, more preferably 1part by mass or more, still more preferably 3 parts by mass or more,even still more preferably 5 parts by mass or more, and is preferably 30parts by mass or less, more preferably 20 parts by mass or less, stillmore preferably 10 parts by mass or less, even still more preferably 7parts by mass or less, with respect to 100 parts by mass of the olefin,from the viewpoint of catalytic activity and selectively obtainingepoxides.

The reaction can be carried out in a liquid phase in the presence orabsence of a solvent. It is preferable to use a solvent that is liquidat the temperature and pressure during the reaction and is substantiallyinactive with respect to the raw materials and products. The reactioncan also be carried out, for example, in the form of a suspended bed ora fixed bed, by a batch method, a semi-continuous method or a continuousmethod. The reaction is preferably carried out in an atmosphere of aninert gas such as nitrogen. The order of charging the raw materials suchas olefin, solid oxidation catalyst, and oxidant (for example, hydrogenperoxide) into the reaction vessel (order of charging) is arbitrary, andthese may be charged all at once. In the case of performing anepoxidation of an olefin having a low reactivity, the reaction can beprogressed efficiently by adopting a method of dropping an olefin into amixture containing a solid oxidation catalyst and an oxidant (forexample, hydrogen peroxide).

The reaction temperature is usually about 0 to 120° C., but from theviewpoint of reactivity, safety, and selectively obtaining epoxides, thereaction temperature is preferably 40° C. or higher, more preferably 50°C. or higher, still more preferably 60° C. or higher, and is preferably90° C. or lower, more preferably 85° C. or lower, still more preferably80° C. or lower.

The reaction pressure may be a pressure sufficient to keep the reactionmixture in a liquid state but is preferably a normal pressure from theviewpoint of safety.

The reaction time varies depending on the type of the solid oxidationcatalyst and the olefin used, the concentration of the oxidant (forexample, hydrogen peroxide), the reaction temperature, etc., but isusually several minutes to 40 hours. From the viewpoint of reactivityand productivity, the reaction time is preferably 0.5 hours or more,more preferably 1 hour or more, still more preferably 1.5 hours or more,even still more preferably 2 hours or more, and is preferably 30 hoursor less, more preferably 20 hours or less, still more preferably 10hours or less, even still more preferably 7 hours or less.

After the reaction, the solid oxidation catalyst is separated byfiltration, and then water and the solvent are removed by means such asextraction or distillation to obtain a desired epoxyalkane. The solidoxidation catalyst separated by filtration can be used repeatedly.

The present invention and preferred embodiments of the present inventionare described below.

<1>

A method for producing an epoxyalkane, which method comprises reactingan olefin with an oxidant in the presence of a solid oxidation catalyst,wherein

the solid oxidation catalyst comprises a transition metal and a carrierthat supports the transition metal, and

the carrier is a metal oxide having a silyl group represented by thefollowing general formula (1):

R¹R²R³Si—  (1)

wherein R¹, R², and R³ are each independently a single bond, ahydrocarbon group, a halogenated hydrocarbon group, an alkoxy group, ora halogen, and at least one of R¹, R², and R³ is a hydrocarbon grouphaving 3 or more carbon atoms or a halogenated hydrocarbon group having3 or more carbon atoms.

<2>

The method for producing an epoxyalkane according to <1>, wherein thetransition metal is supported on the carrier in the form of a simplesubstance, a compound, or an ion.

<3>

The method for producing an epoxyalkane according to <1> or <2>, whereinthe transition metal is preferably a metal element of groups 4 to 8,more preferably a group 6 metal element, still more preferably W.

<4>

The method for producing an epoxyalkane according to <2> or <3>, whereinthe transition metal compound is a tungsten compound.

<5>

The method for producing an epoxyalkane according to <4>, wherein thetungsten compound is tungstic acid or a salt thereof.

<6>

The method for producing an epoxyalkane according to any one of <1> to<5>, wherein the metal oxide is preferably an oxide containing a metalelement having a period of 3 to 5 cycles in the periodic table, morepreferably an oxide containing one or more metal elements selected fromMg, Al, Si, Ti, Fe, Zn, Ga, Y, Zr, and Sn, still more preferably anoxide containing Al.

<7>

The method for producing an epoxyalkane according to any one of <1> to<6>, wherein the metal oxide is a composite with phosphonic acid.

<8>

The method for producing an epoxyalkane according to any one of <1> to<7>, wherein the metal oxide preferably contains phosphoric acid, morepreferably contains Al and/or phosphoric acid, and is still morepreferably aluminum phosphate.

<9>

The method for producing an epoxyalkane according to <7> or <8>, whereinthe phosphonic acid is preferably an organic phosphonic acid having asaturated or unsaturated hydrocarbon group having 1 or more and 18 orless carbon atoms, more preferably one or more selected from analkylphosphonic acid having an alkyl group of 2 to 18 carbon atoms andan aryl phosphonic acid, still more preferably an alkylphosphonic acidhaving an alkyl group of 2 to 18 carbon atoms.

<10>

The method for producing an epoxyalkane according to any one of <7> to<9>, wherein the method for preparing the composite of the metal oxideand the phosphonic acid is a precipitation method.

<11>

The method for producing an epoxyalkane according to <10>, wherein thecomposite of the metal oxide and the phosphonic acid is a composite ofaluminum phosphate and an organic phosphonic acid (RPOO₂AlPO₄).

<12>

The method for producing an epoxyalkane according to <11>, wherein anaqueous solution (S) containing a water-soluble aluminum salt,phosphoric acid, and an organic phosphonic acid is mixed with an alkali(T) in the precipitation method.

<13>

The method for producing an epoxyalkane according to <12>, wherein themolar ratio (Al/P) of Al in the water-soluble aluminum salt to P in thephosphoric acid and organic phosphonic acid is preferably 0.6 or more,more preferably 0.7 or more, still more preferably 0.8 or more, evenstill more preferably 0.9 or more, and is preferably 10 or less, morepreferably 5 or less, still more preferably 2 or less, even still morepreferably less than 1.

<14>

The method for producing an epoxyalkane according to <12> or <13>,wherein the molar ratio of the organic phosphonic acid to the phosphoricacid (organic phosphonic acid/phosphoric acid) is preferably 0.05 ormore, more preferably 0.1 or more, still more preferably 0.2 or more,even still more preferably 0.3 or more, and is preferably 5 or less,more preferably 3 or less, still more preferably 1 or less, even stillmore preferably 0.5 or less.

<15>

The method for producing an epoxyalkane according to any one of <12> to<14>, wherein the alkali (T) is ammonia.

<16>

The method for producing an epoxyalkane according to any one of <12> to<15>, wherein the method of mixing the aqueous solution (S) and thealkali (T) is a method of dropping the alkali (T) into the aqueoussolution (S).

<17>

The method for producing an epoxyalkane according to <16>, wherein thedropping time is preferably 0.5 hours or more, more preferably 1 hour ormore, still more preferably 2 hours or more, even still more preferably3 hours or more, and is preferably 15 hours or less, more preferably 10hours or less, still more preferably 5 hours or less.

<18>

The method for producing an epoxyalkane according to <16> or <17>,wherein the reaction temperature is preferably 20° C. or higher, morepreferably 25° C. or higher, and is preferably 80° C. or lower, morepreferably 60° C. or lower, still more preferably 40° C. or lower.

<19>

The method for producing an epoxyalkane according to any one of <12> to<18>, wherein the pH when mixing the aqueous solution (S) and the alkali(T) is preferably 4.0 or more, more preferably 4.5 or more, still morepreferably 5.0 or more, and is preferably 10.0 or less, more preferably8.0 or less, still more preferably 6.0 or less.

<20>

The method for producing an epoxyalkane according to any one of <12> to<19>, wherein the precipitate obtained by mixing the aqueous solution(S) and the alkali (T) is aged in the reaction solution.

<21>

The method for producing an epoxyalkane according to <20>, wherein theaging time is preferably 0.5 hours or more, more preferably 1 hour ormore, and is preferably 10 hours or less, more preferably 5 hours orless, still more preferably 3 hours or less.

<22>

The method for producing an epoxyalkane according to <20> to <21>,wherein the precipitate is calcined.

<23>

The method for producing an epoxyalkane according to <22>, wherein thecalcination temperature is preferably 250° C. or higher, more preferably300° C. or higher, still more preferably 350° C. or higher, and ispreferably 500° C. or lower, more preferably 450° C. or lower, stillmore preferably 400° C. or lower.

<24>

The method for producing an epoxyalkane according to <22> or <23>,wherein the calcination time is preferably 1 hour or more, morepreferably 2 hours or more, still more preferably 3 hours or more, andis preferably 10 hours or less, more preferably 7 hours or less, stillmore preferably 5 hours or less.

<25>

The method for producing an epoxyalkane according to any one of <22> to<24>, wherein the calcination is carried out in the presence of air oroxygen.

<26>

The method for producing an epoxyalkane according to any one of <1> to<25>, wherein the carrier is in the form of a powder, and an averageparticle size of the powder is preferably 1 μm or more, more preferably3 μm or more, still more preferably 5 μm or more, even still morepreferably 7 μm or more, and is preferably 300 μm or less, morepreferably 200 μm or less, still more preferably 100 μm or less, evenstill more preferably 30 μm or less.

<27>

The method for producing an epoxyalkane according to any one of <1> to<25>, wherein the carrier is in the form of granules, and an averageparticle size of granules is preferably 0.2 mm or more, more preferably0.4 mm or more, still more preferably 0.6 mm or more, and is preferably2.0 mm or less, more preferably 1.3 mm or less, still more preferably0.8 mm or less.

<28>

The method for producing an epoxyalkane according to any one of <1> to<25>, wherein the carrier is in the form of a noodle, and a diameter ofthe noodle is preferably 1.0 mm or more, more preferably 1.2 mm or more,still more preferably 1.4 mm or more, and is preferably 2.5 mm or less,more preferably 2.0 mm or less, still more preferably 1.5 mm or less.

<29>

The method for producing an epoxyalkane according to any one of <1> to<25> and <28>, wherein the carrier is in the form of a noodle, and alength of the noodle is preferably 2 mm or more, more preferably 3 mm ormore, and is preferably 8 mm or less, more preferably 6 mm or less,still more preferably 4 mm or less.

<30>

The method for producing an epoxyalkane according to any one of <1> to<25>, wherein the carrier is in the form of a pellet, and a length ofthe pellet is preferably 1.5 mm or more, more preferably 2.0 mm or more,still more preferably 2.5 mm or more, and is preferably 5.0 mm or less,more preferably 4.0 mm or less, still more preferably 3.0 mm or less.

<31>

The method for producing an epoxyalkane according to any one of <1> to<30>, wherein the specific surface area of the carrier is preferably 30m²/g or more, more preferably 50 m²/g or more, still more preferably 80m²/g or more, and is preferably 250 m²/g or less, more preferably 190m²/g or less, still more preferably 140 m²/g or less.

<32>

The method for producing an epoxyalkane according to any one of <1> to<31>, wherein the average pore diameter of the carrier is preferably 2nm or more, more preferably 3 nm or more, still more preferably 4 nm ormore, and is preferably 15 nm or less, more preferably 10 nm or less,still more preferably 7 nm or less.

<33>

The method for producing an epoxyalkane according to any one of <1> to<32>, wherein the solid oxidation catalyst is prepared by supporting thetransition metal on the metal oxide and then silylating the metal oxidewith a silylating agent.

<34>

The method for producing an epoxyalkane according to <33>, wherein thetransition metal is supported on the metal oxide by an impregnationmethod.

<35>

The method for producing an epoxyalkane according to <33> or <34>,wherein a transition metal-supported metal oxide in which the transitionmetal is supported on the metal oxide is calcined.

<36>

The method for producing an epoxyalkane according to <35>, wherein thecalcination temperature is preferably 150° C. or higher, more preferably200° C. or higher, still more preferably 300° C. or higher, and ispreferably 500° C. or lower, more preferably 450° C. or lower, stillmore preferably 400° C. or lower.

<37>

The method for producing an epoxyalkane according to <35> or <36>,wherein the calcination time is preferably 1 hour or more, morepreferably 2 hours or more, still more preferably 3 hours or more, andis preferably 10 hours or less, more preferably 7 hours or less, stillmore preferably 5 hours or less.

<38>

The method for producing an epoxyalkane according to any one of <35> to<37>, wherein the calcination is carried out in the presence of air oroxygen.

<39>

The method for producing an epoxyalkane according to any one of <33> to<38>, wherein the silylating agent is a silylating agent represented bythe following general formula (2):

R¹R²R³SiX   (2)

wherein R¹, R², and R³ are each independently a hydrocarbon group, ahalogenated hydrocarbon group, an alkoxy group, or a halogen; at leastone of R¹, R², and R³ is a hydrocarbon group having 3 or more carbonatoms or a halogenated hydrocarbon group having 3 or more carbon atoms;and X is an alkoxy group or a halogen.

<40>

The method for producing an epoxyalkane according to any one of <1> to<39>, wherein the hydrocarbon group is a saturated or unsaturatedaliphatic hydrocarbon group, a saturated or unsaturated alicyclichydrocarbon group or an aromatic hydrocarbon group.

<41>

The method for producing an epoxyalkane according to <40>, wherein thenumber of carbon atoms of the aliphatic hydrocarbon group or thealicyclic hydrocarbon group is preferably 3 or more, more preferably 6or more, still more preferably 8 or more, and is preferably 22 or less,more preferably 18 or less, still more preferably 12 or less.

<42>

The method for producing an epoxyalkane according to <40> or <41>,wherein the aromatic hydrocarbon group is a phenyl group, a benzylgroup, a tolyl group, a xylyl group, a naphthyl group or a biphenylgroup.

<43>

The method for producing an epoxyalkane according to any one of <1> to<42>, wherein the halogenated hydrocarbon group is one in which one ormore hydrogens of the hydrocarbon group are substituted with fluorine,chlorine, bromine or iodine.

<44>

The method for producing an epoxyalkane according to any one of <1> to<43>, wherein the alkoxy group is an alkoxy group having 1 to 6 carbonatoms.

<45>

The method for producing an epoxyalkane according to any one of <1> to<44>, wherein the alkoxy group has preferably 4 or less carbon atoms,more preferably 2 or less carbon atoms, still more preferably 1 carbonatom.

<46>

The method for producing an epoxyalkane according to any one of <1> to<45>, wherein the halogen is fluorine, chlorine, bromine or iodine, andis preferably chlorine.

<47>

The method for producing an epoxyalkane according to any one of <1> to<46>, wherein at least one of R¹, R², and R³ is a hydrocarbon grouphaving 3 or more carbon atoms or a halogenated hydrocarbon group having3 or more carbon atoms, and the number of carbon atoms is preferably 6or more, more preferably 8 or more, and is preferably 22 or less, morepreferably 18 or less, still more preferably 12 or less.

<48>

The method for producing an epoxyalkane according to any one of <33> to<47>, wherein a silylation is carried out by a method of reacting themetal oxide supporting the transition metal with the silylating agent ina solvent.

<49>

The method for producing an epoxyalkane according to <48>, wherein thesolvent is at least one non-polar organic solvent selected from hexane,ether, benzene, and toluene.

<50>

The method for producing an epoxyalkane according to <48> or <49>,wherein the blending amount of the silylating agent is preferably 0.05parts by mass or more, more preferably 0.2 parts by mass or more, stillmore preferably 0.4 parts by mass or more, even still more preferably0.6 parts by mass or more, and is preferably 40 parts by mass or less,more preferably 30 parts by mass or less, still more preferably 20 partsby mass or less, even still more preferably 10 parts by mass or less,furthermore preferably 8 parts by mass or less, with respect to 100parts by mass of the metal oxide supporting the transition metal.

<51>

The method for producing an epoxyalkane according to any one of <48> to<50>, wherein the reaction temperature is preferably 70° C. or higher,more preferably 80° C. or higher, still more preferably 90° C. orhigher, and is preferably 120° C. or lower, more preferably 110° C. orlower.

<52>

The method for producing an epoxyalkane according to any one of <48> to<51>, wherein the reaction time is preferably 0.5 hours or more, morepreferably 1 hour or more, still more preferably 1.5 hours or more, evenstill more preferably 2 hours or more, and is preferably 30 hours orless, more preferably 20 hours or less, still more preferably 10 hoursor less, even still more preferably 7 hours or less.

<53>

The method for producing an epoxyalkane according to any one of <1> to<52>, wherein the amount of the transition metal supported in the solidoxidation catalyst is preferably 0.5% by mass or more, more preferably1% by mass or more, still more preferably 3% by mass or more, even stillmore preferably 5% by mass or more, and is preferably 50% by mass orless, more preferably 25% by mass or less, still more preferably 15% bymass or less, even still more preferably 10% by mass or less.

<54>

The method for producing an epoxyalkane according to any one of <1> to<53>, wherein the wetting tension of the solid oxidation catalyst ispreferably 30 mN/m or more, more preferably 40 mN/m or more, still morepreferably 50 mN/m or more, even still more preferably 55 mN/m or more,and is preferably 73 mN/m or less, more preferably 70 mN/m or less,still more preferably 65 mN/m or less, even still more preferably 60mN/m or less.

<55>

The method for producing an epoxyalkane according to any one of <1> to<54>, wherein the catalytic specific surface area of the solid oxidationcatalyst is preferably 30 m²/g or more, more preferably 50 m²/g or more,still more preferably 80 m²/g or more, and is preferably 250 m²/g orless, more preferably 190 m²/g or less, still more preferably 140 m²/gor less.

<56>

The method for producing an epoxyalkane according to any one of <1> to<55>, wherein the average pore size of the solid oxidation catalyst ispreferably 2 nm or more, more preferably 3 nm or more, still morepreferably 4 nm or more, and is preferably 15 nm or less, morepreferably 10 nm or less, still more preferably 7 nm or less.

<57>

The method for producing an epoxyalkane according to any one of <1> to<56>, wherein the particle size of the solid oxidation catalyst ispreferably 1 μm or more, more preferably 3 μm or more, still morepreferably 5 μm or more, even still more preferably 7 μm or more, and ispreferably 300 μm or less, more preferably 200 μm or less, still morepreferably 100 μm or less, even still more preferably 30 μm or less.

<58>

The method for producing an epoxyalkane according to any one of <1> to<57>, wherein the olefin is a linear or branched unsaturatedhydrocarbon.

<59>

The method for producing an epoxyalkane according to any one of <1> to<58>, wherein the carbon number of the olefin (excluding the carbonnumber of the substituent) is preferably 8 or more, more preferably 12or more, still more preferably 14 or more, even still more preferably 16or more, and preferably 22 or less, more preferably 20 or less, stillmore preferably 18 or less.

<60>

The method for producing an epoxyalkane according to any one of <1> to<59>, wherein the oxidant is a peroxide.

<61>

The method for producing an epoxyalkane according to any one of <1> to<60>, wherein the oxidant is hydrogen peroxide.

<62>

The method for producing an epoxyalkane according to <61>, wherein theconcentration of hydrogen peroxide in the aqueous solution is preferably10% by mass or more, more preferably 25% by mass or more, still morepreferably 40% by mass or more, and is preferably 85% by mass or less,more preferably 70% by mass or less, still more preferably 65% by massor less.

<63>

The method for producing an epoxyalkane according to any one of <1> to<62>, wherein the amount of the oxidant used is preferably 0.2equivalents or more, more preferably 0.5 equivalents or more, still morepreferably 0.8 equivalents or more, even still more preferably 1.0equivalent or more, and is preferably 10 equivalents or less, morepreferably 5 equivalents or less, still more preferably 3 equivalents orless, even still more preferably 1.5 equivalents or less, with respectto 1 equivalent of the olefin.

<64>

The method for producing an epoxyalkane according to any one of <1> to<63>, wherein the amount of the solid oxidation catalyst used ispreferably 0.5 parts by mass or more, more preferably 1 part by mass ormore, still more preferably 3 parts by mass or more, even still morepreferably 5 parts by mass or more, and is preferably 30 parts by massor less, more preferably 20 parts by mass or less, still more preferably10 parts by mass or less, even still more preferably 7 parts by mass orless, with respect to 100 parts by mass of the olefin.

<65>

The method for producing an epoxyalkane according to any one of <1> to<59>, wherein the carbon number of the olefin (excluding the carbonnumber of the substituent) is 8 or more and 22 or less, the oxidant ishydrogen peroxide, the concentration of hydrogen peroxide in the aqueoussolution is 10% by mass or more and 85% by mass or less, the amount ofhydrogen peroxide used is 0.2 equivalents or more and 10 equivalents orless with respect to 1 equivalent of the olefin, and the amount of thesolid oxidation catalyst used is 0.5 parts by mass or more and 30 partsby mass or less with respect to 100 parts by mass of the olefin.

<66>

The method for producing an epoxyalkane according to any one of <1> to<59>, wherein the carbon number of the olefin (excluding the carbonnumber of the substituent) is 12 or more and 20 or less, the oxidant ishydrogen peroxide, the concentration of hydrogen peroxide in the aqueoussolution is 25% by mass or more and 70% by mass or less, the amount ofhydrogen peroxide used is 0.5 equivalents or more and 5 equivalents orless with respect to 1 equivalent of the olefin, and the amount of thesolid oxidation catalyst used is 1 parts by mass or more and 20 parts bymass or less with respect to 100 parts by mass of the olefin.

<67>

The method for producing an epoxyalkane according to any one of <1> to<59>, wherein the carbon number of the olefin (excluding the carbonnumber of the substituent) is 14 or more and 18 or less, the oxidant ishydrogen peroxide, the concentration of hydrogen peroxide in the aqueoussolution is 40% by mass or more and 65% by mass or less, the amount ofhydrogen peroxide used is 0.8 equivalents or more and 3 equivalents orless with respect to 1 equivalent of the olefin, and the amount of thesolid oxidation catalyst used is 3 parts by mass or more and 10 parts bymass or less with respect to 100 parts by mass of the olefin.

<68>

The method for producing an epoxyalkane according to any one of <1> to<59>, wherein the carbon number of the olefin (excluding the carbonnumber of the substituent) is 16 or more and 18 or less, the oxidant ishydrogen peroxide, the concentration of hydrogen peroxide in the aqueoussolution is 40% by mass or more and 65% by mass or less, the amount ofhydrogen peroxide used is 1.0 equivalents or more and 1.5 equivalents orless with respect to 1 equivalent of the olefin, and the amount of thesolid oxidation catalyst used is 5 parts by mass or more and 7 parts bymass or less with respect to 100 parts by mass of the olefin.

<69>

The method for producing an epoxyalkane according to any one of <1> to<68>, wherein the reaction temperature when reacting the olefin with theoxidant is preferably 40° C. or higher, more preferably 50° C. orhigher, still more preferably 60° C. or higher, and is preferably 90° C.or lower, more preferably 85° C. or lower, still more preferably 80° C.or lower.

<70>

The method for producing an epoxyalkane according to any one of <1> to<69>, wherein the reaction time when reacting the olefin with theoxidant is preferably 0.5 hours or more, more preferably 1 hour or more,still more preferably 1.5 hours or more, even still more preferably 2hours or more, and is preferably 30 hours or less, more preferably 20hours or less, still more preferably 10 hours or less, even still morepreferably 7 hours or less.

<71>

A solid oxidation catalyst that is used in a method for producing anepoxyalkane by reacting an olefin with an oxidant, wherein

the solid oxidation catalyst comprises a transition metal and a carrierthat supports the transition metal, and

the carrier is a metal oxide having a silyl group represented by thefollowing general formula (1):

R¹R²R³Si—  (1)

wherein R¹, R², and R³ are each independently a single bond, ahydrocarbon group, a halogenated hydrocarbon group, an alkoxy group, ora halogen, and at least one of R¹, R², and R³ is a hydrocarbon grouphaving 3 or more carbon atoms or a halogenated hydrocarbon group having3 or more carbon atoms.

<72>

The solid oxidation catalyst according to <71>, wherein the hydrocarbongroup is a saturated or unsaturated aliphatic hydrocarbon group, asaturated or unsaturated alicyclic hydrocarbon group or an aromatichydrocarbon group.

<73>

The solid oxidation catalyst according to <72>, wherein the number ofcarbon atoms of the aliphatic hydrocarbon group or the alicyclichydrocarbon group is preferably 3 or more, more preferably 6 or more,still more preferably 8 or more, and is preferably 22 or less, morepreferably 18 or less, still more preferably 12 or less.

<74>

The solid oxidation catalyst according to <72>or <73>, wherein thearomatic hydrocarbon group is a phenyl group, a benzyl group, a tolylgroup, a xylyl group, a naphthyl group or a biphenyl group.

<75>

The solid oxidation catalyst according to any one of <71> to <74>,wherein the halogenated hydrocarbon group is one in which one or morehydrogens of the hydrocarbon group are substituted with fluorine,chlorine, bromine or iodine.

<76>

The solid oxidation catalyst according to any one of <71> to <75>,wherein the alkoxy group is an alkoxy group having 1 to 6 carbon atoms.

<77>

The solid oxidation catalyst according to any one of <71> to <76>,wherein the alkoxy group has preferably 4 or less carbon atoms, morepreferably 2 or less carbon atoms, still more preferably 1 carbon atom.

<78>

The solid oxidation catalyst according to any one of <71> to <77>,wherein the halogen is fluorine, chlorine, bromine or iodine, and ispreferably chlorine.

<79>

The solid oxidation catalyst according to any one of <71> to <78>,wherein at least one of R¹, R², and R³ is a hydrocarbon group having 3or more carbon atoms or a halogenated hydrocarbon group having 3 or morecarbon atoms, and the number of carbon atoms is preferably 6 or more,more preferably 8 or more, and is preferably 22 or less, more preferably18 or less, still more preferably 12 or less.

<80>

The solid oxidation catalyst according to any one of <71> to <79>,wherein the transition metal is supported on the carrier in the form ofa simple substance, a compound, or an ion.

<81>

The solid oxidation catalyst according to any one of <71> to <80>,wherein the transition metal is preferably a metal element of groups 4to 8, more preferably a group 6 metal element, still more preferably W.

<82>

The solid oxidation catalyst according to <80> or <81>, wherein thetransition metal compound is a tungsten compound.

<83>

The solid oxidation catalyst according to <82>, wherein the tungstencompound is tungstic acid or a salt thereof.

<84>

The solid oxidation catalyst according to any one of <71> to <83>,wherein the metal oxide is preferably an oxide containing a metalelement having a period of 3 to 5 cycles in the periodic table, morepreferably an oxide containing one or more metal elements selected fromMg, Al, Si, Ti, Fe, Zn, Ga, Y, Zr, and Sn, still more preferably anoxide containing Al.

<85>

The solid oxidation catalyst according to any one of <71> to <84>,wherein the metal oxide is a composite with phosphoric acid.

<86>

The solid oxidation catalyst according to any one of <71> to <85>,wherein the metal oxide preferably contains phosphoric acid, morepreferably contains Al and/or phosphoric acid, and is still morepreferably aluminum phosphate.

<87>

The solid oxidation catalyst according to <85> or <86>, wherein thephosphonic acid is preferably an organic phosphonic acid having asaturated or unsaturated hydrocarbon group having 1 or more and 18 orless carbon atoms, more preferably one or more selected from analkylphosphonic acid having an alkyl group of 2 to 18 carbon atoms andan aryl phosphonic acid, still more preferably an alkylphosphonic acidhaving an alkyl group of 2 to 18 carbon atoms.

<88>

The solid oxidation catalyst according to any one of <71> to <87>,wherein the oxidant is a peroxide.

<89>

The solid oxidation catalyst according to any one of <71> to <88>,wherein the oxidant is hydrogen peroxide.

EXAMPLES

Hereinafter, the present invention will be specifically described basedon Examples. Unless otherwise specified in the table, the content “%” ofeach component indicates % by mass. In addition, various measurementmethods are as follows.

Calculation of Supported Amount of Tungsten

The supported amount (% by mass) of tungsten in the solid oxidationcatalyst was calculated from the charged amount of the raw materials.

Measurement of Olefin Conversion Rate

After converting the reaction solution to TMS using a TMSI-H (GLSciences Inc.), a column “Ultra ALLOY-1HT” (manufactured by FrontierLaboratories Ltd.: Capillary column 30.0 m×250 μm×0.15 mm) was attachedto a gas chromatograph analyzer “GC6850” (manufactured by Agilent).Analysis was performed using a hydrogen flame ion detector (FID) underthe conditions of an injection temperature of 300° C., a detectortemperature of 350° C., and a He flow rate of 4.6 mL/min, and then theproduct was quantified. The olefin conversion rate was calculated by thefollowing formula.

Olefin conversion rate (%)=[100−(Amount of olefin)]/[(Amount ofolefin)+(Amount of epoxide)+(Total amount of by-products)]×100

Measurement of Selectivity for Epoxides

The selectivity for epoxides was calculated by the following formula.For each amount in the formula, the value obtained from the gaschromatograph analysis of the olefin conversion rate measurement wasused.

Selectivity for epoxides (%)=(Amount of epoxide)/[(Amount ofolefin)+(Amount of epoxide)+(Total amount of by-products)]×100

Example 1 Preparation of Composite of Ethylphosphonic Acid With AluminumPhosphate

In a 2 L separable flask, 600 g of ion-exchange water, 7.4 g (0.07 mol)of ethylphosphonic acid, 20.7 g (0.18 mol) of 85% aqueous phosphoricacid solution, and a solution prepared by dissolving 84 g (0.2 mol) ofAl(NO₃)₃.9H₂O in 150 g of ion-exchange water were charged, and then astirrer, a pH electrode, a thermometer, and a dropping tube holder wereattached to the flask. After stirring the mixture at 25° C. and 400 rpmfor 10 minutes, a 10% aqueous NH₃ solution was added dropwise at 25° C.using a dropping tube pump at a rate of 0.6 mL/min over the period of 3hours until the pH reached 5. After completion of the dropping, themixture was aged for 1 hour with stirring. Thereafter, a white cakecollected by filtration under reduced pressure was washed five timeswith 1.5 L of ion-exchange water until the electric conductivity reached40 mS/m (each stirring was performed at 700 rpm for 1 hour). Then, theobtained cake was dried at 120° C. overnight (about 15 hours),pulverized in a coffee mill, and further calcined at 350° C. for 3 hoursto obtain a composite (EtPOO₂Al PO₄) of ethylphosphonic acid withaluminum phosphate.

Preparation of W-Supported Composite

In a 300 mL four-necked flask, 200 g of ion-exchange water and 1.0 g oftungstic acid (H₂WO₄) were charged, and a 28% aqueous NH₃ solution wasadded little by little until the pH reached 7 while stirring, thereby toobtain an aqueous ammonium tungstate solution. The prepared aqueousammonium tungstate solution (200 g) was added to a 1 L round-bottomflask charged with 20 g of the composite, and the flask was immersed inan oil bath set at 63° C. and stirred for 0.5 hours. Next, water wasremoved from the flask by an evaporator to collect a solid. The obtainedsolid was dried at 120° C. overnight (about 15 hours), pulverized by acoffee mill, and calcined at 350° C. for 3 hours to obtain a W-supportedcomposite (W/EtPOO₂AlPO₄) having tungsten supported on a composite.

Preparation of Solid Oxidation Catalyst

A 300 mL round-bottom flask was charged with 10 g of a W-supportedcomposite (W/EtPOO₂AlPO₄), 157 g of toluene, and 1.0 g oftrimethoxyoctenylsilane ((CH₃O)₃Si(CH₂)₆CH═CH₂) as a silylating agentand was equipped with a stirrer and a thermometer. Then, the mixture wasrefluxed and stirred at 300 rpm for 7 hours. After allowing to stand forcooling, the mixture was filtered under reduced pressure to collect asolid, which was washed with 150 ml of ion-exchange water three times.After that, the solid was dried at 120° C. overnight (about 15 hours) toobtain a solid oxidation catalyst (W/EtPOO₂AlPO₄Si(CH₂)₆CH═CH₂).

Synthesis of Epoxyalkane

In a 100 mL four-neck flask, 2 g of the prepared solid oxidationcatalyst (W/EtPOO₂AlPO₄Si(CH₂)₆CH═CH₂) and 40 g (0.18 mol) of1-hexadecene were charged. The flask was equipped with a stirrer, athermometer, and an N₂ flow, and 12 g (0.21 mol, 1.2 equivalents/1equivalent of olefin) of 60% aqueous hydrogen peroxide was added in theflask. Thereafter, the flask was immersed in an oil bath set at 80° C.and the reaction was performed for 8 hours to synthesizeepoxyhexadecane. The stirring was stopped on the way and sampling wasperformed every 0.5 to 2 hours to determine the olefin conversion rateand the selectivity for epoxides by the method described above. Table 1shows the olefin conversion rate and the selectivity for epoxides at thereaction times shown in Table 1.

Example 2

A solid oxidation catalyst (W/EtPOO₂AlPO₄SiC₈H₁₇) was obtained in thesame manner as in Example 1 except that 0.2 g of trimethoxyoctylsilanewas used as the silylating agent in the preparation of the solidoxidation catalyst.

Then, using the solid oxidation catalyst (W/EtPOO₂AlPO₄SiC₈H₁₇),epoxyhexadecane was synthesized by the same method as in Example 1except that the reaction time was changed to that shown in Table 1.Then, an olefin conversion rate and a selectivity for epoxides weredetermined and the results were described in Table 1.

Example 3

A solid oxidation catalyst (W/EtPOO₂AlPO₄SiC₈H₁₇) was obtained in thesame manner as in Example 1 except that 1.0 g of trimethoxyoctylsilanewas used as the silylating agent in the preparation of the solidoxidation catalyst.

Then, using the solid oxidation catalyst (W/EtPOO₂AlPO₄SiC₈H₁₇),epoxyhexadecane was synthesized by the same method as in Example 1except that the reaction time was changed to that shown in Table 1.Then, an olefin conversion rate and a selectivity for epoxides weredetermined and the results were described in Table 1.

Examples 4 to 11 and Comparative Example 2 Preparation of AluminumPhosphate

In a 2 L separable flask, 600 g of ion-exchange water, 25.8 g (0.22 mol)of an 85% aqueous phosphoric acid solution, and a solution in which 84 g(0.2 mol) of Al(NO₃)₃.9H₂O was dissolved in 150 g of ion-exchange waterwere charged, and a stirrer, a pH electrode, a thermometer, and adropping tube holder were attached to the flask. After stirring themixture at 25° C. and 400 rpm for 10 minutes, a 10% aqueous NH₃ solutionwas added dropwise at 25° C. using a dropping tube pump at a rate of 0.6mL/min over 3 hours until the pH reached 5. After completion of thedropwise addition, the mixture was aged for 1 hour with stirring.Thereafter, a white cake collected by filtration under reduced pressurewas washed five times with 1.5 L of ion-exchange water until theelectric conductivity reached 40 mS/m (each stirring was performed at700 rpm for 1 hour). Then, the obtained cake was dried at 120° C.overnight (about 15 hours), pulverized by a coffee mill, and furthercalcined at 350° C. for 3 hours to obtain aluminum phosphate (AlPO₄).

Preparation of W-Supported Aluminum Phosphate

In a 300 mL four-necked flask, 200 g of ion-exchange water and 1.0 g oftungstic acid (H₂WO₄) were charged, and a 28% aqueous NH₃ solution wasadded little by little until the pH reached 7 while stirring, thereby toobtain an aqueous ammonium tungstate solution. The prepared aqueousammonium tungstate solution (200 g) was added to a 1 L round-bottomflask charged with 20 g of the prepared aluminum phosphate, and theflask was immersed in an oil bath set at 63° C. and stirred for 0.5hours. Next, water was removed from the flask by an evaporator tocollect a solid. The obtained solid was dried at 120° C. overnight(about 15 hours), pulverized by a coffee mill, and calcined at 350° C.for 3 hours to obtain a W-supported aluminum phosphate (W/AlPO₄) havingtungsten supported on aluminum phosphate.

Preparation of Solid Oxidation Catalyst

Each solid oxidation catalyst (W/AlPO₄SiR) shown in Table 1 was obtainedin the same manner as in Example 1 except that the silylating agent andthe blending amount shown in Table 1 were used.

Synthesis of Epoxyalkane

Epoxyhexadecane was synthesized in the same manner as in Example 1except that each solid oxidation catalyst (W/AlPO₄SiR) shown in Table 1was used and the reaction time was changed to that shown in Table 1.Then, an olefin conversion rate and a selectivity for epoxides weredetermined and the results were shown in Table 1. It should be notedthat in Example 9, 200 parts by mass of t-butyl alcohol was used withrespect to 100 parts by mass of 1-hexadecene.

Comparative Example 1 Synthesis of Epoxyalkane

Epoxyhexadecane was synthesized in the same manner as in Example 1except that the prepared W-supported aluminum phosphate (W/AlPO₄) wasused and the reaction time was changed to that shown in Table 1. Then,an olefin conversion rate and a selectivity for epoxides were determinedand the results were shown in Table 1.

Comparative Example 3 Preparation of Catalyst

A round bottom flask having a capacity of 30 cm³ was charged with 0.387g (3 mmol) of quinoline, 0.596 g (3 mmol) ofchloropropyltrimethoxysilane and 5 cm³ of petroleum ether, and themixture was vigorously stirred in a hot water bath at 70° C. under anitrogen atmosphere for 5 hours. After completion of the stirring, 5 cm³of dry ethanol and 3 g of silica gel were added thereto, and the mixturewas vigorously stirred at the same temperature for another 1 hour. Aftercompletion of the stirring, the reaction solution was cooled to roomtemperature. Then, 2.88 g (1 mmol) of 12-tungstophosphoric aciddissolved in 5 cm³ of dry ethanol was added, and the mixture wasvigorously stirred at room temperature for 5 hours under a nitrogenatmosphere. After the stirring was completed, the solvent was distilledoff at 50° C. under reduced pressure (133 Pa). Then, the residue wasdried for 5 hours under reduced pressure (133 Pa) under a nitrogenatmosphere to prepare a catalyst.

Synthesis of Epoxyalkane

Epoxyhexadecane was synthesized in the same manner as in Example 1except that the prepared catalyst was used and the reaction time waschanged to that shown in Table 1. Then, an olefin conversion rate and aselectivity for epoxides were determined and the results were shown inTable 1.

TABLE 1 EXAMPLE EXAMPLE EXAMPLE EXAMPLE UNIT 1 2 3 4 CARRIER —EtPOO₂AlPO₄ AlPO₄ SOLID OXIDATION CATALYST — W/EtPOO₂AlPO₄SiR W/AlPO₄SiRR GROUP OF SILYLATING — Octeny Octyl Octyl Propyl AGENT (MeO)₃SiR CARBONNUMBER OF R IN — C8 C8 C8 C3 SILYLATING AGENT (MeO)₃SiR NON-IONIC/IONIC— NON- NON- NON- NON- IONIC IONIC IONIC IONIC AMOUNT OF SILYLATING AGENT% BY 10 2 10 10 (VS W-SUPPORTED CATALYST AMOUNT) MASS W-SUPPORTED AMOUNT% BY 3.5 3.5 3.5 3.5 MASS REACTION TEMPERATURE ° C. 80 80 80 80 REACTIONTIME hr 4 6.25 2 2 OLEFIN CONVERSION RATE % 18 15 18 17 SELECTIVITY FOREPDXIDES % 60 65 59 55 PREPATION OF AMOUNT OF CARRIER ETHYLPHOS g 7.47.4 7.4 — PHONIC ACID MOLE OF mol 0.07 0.07 0.07 — ETHYLPHOS PHONIC ACIDAMOUNT OF g 20.7 20.7 20.7 25.8 85% PHOSPHORIC ACID MOLE OF mol 0.180.18 0.18 0.22 PHOSPHORIC ACID AMOUNT OF g 600 600 600 600 ION- EXCHANGEWATER AMOUNT OF g 84 84 84 84 ALUMINUM NITRATE MOLE OF mol 0.2 0.2 0.20.2 ALUMINUM NITRATE AMOUNT OF g 150 150 150 150 ION- EXCHANGE WATER(FOR DISSOLVING ALUMINUM NITRATE) PREPARATION PREPARATION AMOUNT OF g1.0 1.0 1.0 1.0 OF W- OF H₂WO₄ SUPPORTED IMPREGNATION CATALYST SOLUTIONAMOUNT OF g 200 200 200 200 ION- EXCHANGE WATER IMPREGNATION AMOUNT OF g20 20 20 20 OF W CARRIER H₂WO₄ + NH₃ g 200 200 200 200 AQ. SOLUTIONSILYLATION AMOUNT OF g 10 10 10 10 TREATMENT W-SUPPORTED CATALYST AMOUNTOF g 1.0 0.2 1.0 1.0 SILYLATING AGENT (VS AMOUNT OF SUPPORTED CATALYST)AMOUNT OF g 157 157 157 157 TOLUEN (15.7 TIMES THE AMOUNT OF W-SUPPORTEDCATALYST) EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE 5 6 7 8 9 CARRIERAlPO₄ SOLID OXIDATION CATALYST W/AlPO₄SiR R GROUP OF SILYLATING HexylDodecyl Dodecyl Dodecyl Dodecyl AGENT (MeO)₃SiR CARBON NUMBER OF R IN C6C12 C12 C12 C12 SILYLATING AGENT (MeO)₃SiR NON-IONIC/IONIC NON- NON-NON- NON- NON- IONIC IONIC IONIC IONIC IONIC AMOUNT OF SILYLATING AGENT10 2 5 10 10 (VS W-SUPPORTED CATALYST AMOUNT) W-SUPPORTED AMOUNT 3.5 3.53.5 3.5 3.5 REACTION TEMPERATURE 80 80 80 80 80 REACTION TIME 2 2 4 2 2OLEFIN CONVERSION RATE 14 16 18 15 20 SELECTIVITY FOR EPDXIDES 62 62 5763 57 PREPATION OF AMOUNT OF CARRIER ETHYLPHOS — — — — — PHONIC ACIDMOLE OF — — — — — ETHYLPHOS PHONIC ACID AMOUNT OF 25.8 25.8 25.8 25.825.8 85% PHOSPHORIC ACID MOLE OF 0.22 0.22 0.22 0.22 0.22 PHOSPHORICACID AMOUNT OF 600 600 600 600 600 ION- EXCHANGE WATER AMOUNT OF 84 8484 84 84 ALUMINUM NITRATE MOLE OF 0.2 0.2 0.2 0.2 0.2 ALUMINUM NITRATEAMOUNT OF 150 150 150 150 150 ION- EXCHANGE WATER (FOR DISSOLVINGALUMINUM NITRATE) PREPARATION PREPARATION AMOUNT OF 1.0 1.0 1.0 1.0 1.0OF W- OF H₂WO₄ SUPPORTED IMPREGNATION CATALYST SOLUTION AMOUNT OF 200200 200 200 200 ION- EXCHANGE WATER IMPREGNATION AMOUNT OF 20 20 20 2020 OF W CARRIER H₂WO₄ + NH₃ 200 200 200 200 200 AQ. SOLUTION SILYLATIONAMOUNT OF 10 10 10 10 10 TREATMENT W-SUPPORTED CATALYST AMOUNT OF 1.00.2 0.5 1.0 1.0 SILYLATING AGENT (VS AMOUNT OF SUPPORTED CATALYST)AMOUNT OF 157 157 157 157 157 TOLUEN (15.7 TIMES THE AMOUNT OFW-SUPPORTED CATALYST) COMPARATIVE COMPARATIVE COMPARATIVE EXAMPLEEXAMPLE EXAMPLE EXAMPLE EXAMPLE 10 11 1 2 3 CARRIER AlPO₄ AlPO₄ SOLIDOXIDATION CATALYST W/AlPO₄SiR W/AlPO₄ W/AlPO₄SiR R GROUP OF SILYLATINGOctadcyl CH₂CH₂ — Ethyl Chloropropyl AGENT (MeO)₃SiR (CF₂)₇CF₃ CARBONNUMBER OF R IN C18 C10 — C2 C3 SILYLATING AGENT (MeO)₃SiRNON-IONIC/IONIC NON- NON- NON- NON- IONIC IONIC IONIC IONIC IONIC AMOUNTOF SILYLATING AGENT 2 2 0 10 10 (VS W-SUPPORTED CATALYST AMOUNT)W-SUPPORTED AMOUNT 3.5 3.5 3.5 3.5 37.5 REACTION TEMPERATURE 80 80 80 8080 REACTION TIME 2 8 8 2 8 OLEFIN CONVERSION RATE 15 13 0 16 0SELECTIVITY FOR EPDXIDES 64 65 0 43 0 PREPATION OF AMOUNT OF CARRIERETHYLPHOS — — — — — PHONIC ACID MOLE OF — — — — — ETHYLPHOS PHONIC ACIDAMOUNT OF 25.8 25.8 25.8 25.8 — 85% PHOSPHORIC ACID MOLE OF 0.22 0.220.22 0.22 — PHOSPHORIC ACID AMOUNT OF 600 600 600 600 — ION- EXCHANGEWATER AMOUNT OF 84 84 84 84 — ALUMINUM NITRATE MOLE OF 0.2 0.2 0.2 0.2 —ALUMINUM NITRATE AMOUNT OF 150 150 150 150 — ION- EXCHANGE WATER (FORDISSOLVING ALUMINUM NITRATE) PREPARATION PREPARATION AMOUNT OF 1.0 1.01.0 1.0 — OF W- OF H₂WO₄ SUPPORTED IMPREGNATION CATALYST SOLUTION AMOUNTOF 200 200 200 200 — ION- EXCHANGE WATER IMPREGNATION AMOUNT OF 20 20 2020 — OF W CARRIER H₂WO₄ + NH₃ 200 200 200 200 — AQ. SOLUTION SILYLATIONAMOUNT OF 10 10 — 10 — TREATMENT W-SUPPORTED CATALYST AMOUNT OF 0.2 0.2— 1.0 — SILYLATING AGENT (VS AMOUNT OF SUPPORTED CATALYST) AMOUNT OF 157157 — 157 — TOLUEN (15.7 TIMES THE AMOUNT OF W-SUPPORTED CATALYST)

INDUSTRIAL APPLICABILITY

The method for producing an epoxyalkane and the solid oxidation catalystaccording to the present invention are useful for producing anepoxyalkane for a variety of uses.

1. A method for producing an epoxyalkane, which method comprisesreacting an olefin with an oxidant in the presence of a solid oxidationcatalyst, wherein the solid oxidation catalyst comprises a transitionmetal and a carrier that supports the transition metal, and the carrieris a metal oxide having a silyl group represented by the followinggeneral formula (1):R¹R²R³Si—  (1) wherein R¹, R², and R³ are each independently a singlebond, a hydrocarbon group, a halogenated hydrocarbon group, an alkoxygroup, or a halogen, and at least one of R¹, R², and R³ is a hydrocarbongroup having 3 or more carbon atoms or a halogenated hydrocarbon grouphaving 3 or more carbon atoms.
 2. The method for producing anepoxyalkane according to claim 1, wherein at least one of R¹, R², and R³in the general formula (1) is a hydrocarbon group having 6 or morecarbon atoms or a halogenated hydrocarbon group having 6 or more carbonatoms.
 3. The method for producing an epoxyalkane according to claim 1,wherein the transition metal is W.
 4. The method for producing anepoxyalkane according to claim 1, wherein the metal oxide contains Aland/or phosphoric acid.
 5. The method for producing an epoxyalkaneaccording to claim 1, wherein the metal oxide is AlPO₄.
 6. The methodfor producing an epoxyalkane according to claim 1, wherein the olefinhas 8 or more carbon atoms.
 7. The method for producing an epoxyalkaneaccording to claim 1, wherein the temperature at the time of thereaction is 40° C. or higher and 90° C. or lower.
 8. The method forproducing an epoxyalkane according to claim 1, wherein the oxidant is aperoxide.
 9. The method for producing an epoxyalkane according to claim1, wherein the oxidant is hydrogen peroxide.
 10. A solid oxidationcatalyst that is used in a method for producing an epoxyalkane byreacting an olefin with an oxidant, wherein the solid oxidation catalystcomprises a transition metal and a carrier that supports the transitionmetal, and the carrier is a metal oxide having a silyl group representedby the following general formula (1):R¹R²R³Si—  (₁) wherein R¹, R², and R³ are each independently a singlebond, a hydrocarbon group, a halogenated hydrocarbon group, an alkoxygroup, or a halogen, and at least one of R¹, R², and R³ is a hydrocarbongroup having 3 or more carbon atoms or a halogenated hydrocarbon grouphaving 3 or more carbon atoms.
 11. The solid oxidation catalystaccording to claim 10, wherein at least one of R¹, R², and R³ in thegeneral formula (1) is a hydrocarbon group having 6 or more carbon atomsor a halogenated hydrocarbon group having 6 or more carbon atoms. 12.The solid oxidation catalyst according to claim 10, wherein thetransition metal is W.
 13. The solid oxidation catalyst according toclaim 10, wherein the metal oxide contains Al and/or phosphoric acid.14. The solid oxidation catalyst according to claim 10, wherein themetal oxide is AlPO₄.
 15. The method for producing an epoxyalkaneaccording to claim 2, wherein the transition metal is W.
 16. The methodfor producing an epoxyalkane according to claim 2, wherein the metaloxide contains Al and/or phosphoric acid.
 17. The method for producingan epoxyalkane according to claim 2, wherein the metal oxide is AlPO₄.18. The method for producing an epoxyalkane according to claim 2,wherein the olefin has 8 or more carbon atoms.
 19. The method forproducing an epoxyalkane according to claim 2, wherein the temperatureat the time of the reaction is 40° C. or higher and 90° C. or lower. 20.The method for producing an epoxyalkane according to claim 2, whereinthe oxidant is a peroxide.